CN106448986B - A kind of anisotropy nanocrystalline rare-earth permanent magnet and preparation method thereof - Google Patents
A kind of anisotropy nanocrystalline rare-earth permanent magnet and preparation method thereof Download PDFInfo
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- CN106448986B CN106448986B CN201610847457.5A CN201610847457A CN106448986B CN 106448986 B CN106448986 B CN 106448986B CN 201610847457 A CN201610847457 A CN 201610847457A CN 106448986 B CN106448986 B CN 106448986B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0576—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together pressed, e.g. hot working
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
- H01F41/0266—Moulding; Pressing
Abstract
Anisotropy nanocrystalline rare-earth permanent magnet of the present invention, is RE by chemical formulaaFe100‑a‑b‑cBbTMcIt is nanocrystalline with graphene and/or graphene microchip forms, wherein the content of graphene and/or graphene microchip is 0.01wt%~1wt%, the chemical formula REaFe100‑a‑b‑cBbTMcIn, 28≤a≤33,0.9≤b≤1.35,0.15≤c≤7, at least one of RE Ce, Nd, Pr, Dy, at least one of TM Ga, Co, Cu, Nb, Al, Zr, V, Si, Ti.Present invention also offers the preparation method of above-mentioned anisotropy nanocrystalline rare-earth permanent magnet.The present invention overcomes rare earth permanent-magnetic material RE Fe B magnet slip system numbers are less, the defects of magnetic powder contact surface inclement condition, plastic deformation is difficult, while the magnetic property of rare-earth permanent magnet material is further improved.
Description
Technical field
The invention belongs to rare-earth permanent-magnet material technical field, and in particular to a kind of anisotropy nanocrystalline rare-earth permanent magnet and
Its preparation method.
Background technology
Nd-Fe-B permanent-magnet materials have excellent comprehensive such as high remanent magnetization, high coercivity and high magnetic energy product
Hard magnetic property is closed, is widely used in the fields such as electromechanics, information, communication and medical treatment.Nanocrystalline Nd-Fe-B permanent magnet is steady due to temperature
Qualitative, fracture toughness is superior to traditional micron crystalline substance sintered magnet, is one of the research hotspot of current RE permanent magnetic alloy material.Heat
Pressure/thermal deformation technique is one of effective means for preparing theoretical density anisotropy Nd-Fe-B magnets.Since Nd-Fe-B magnets are deposited
In Anisotropy, i.e. the Young's modulus of a, b axis is much larger than the Young's modulus of c-axis, under the effect of the pressure Nd-Fe-B crystal
By the way that crystal-plane slip, crystal grain rotate, " crystallization of the dissolution and precipitation " mechanism realizes preferential growth, c-axis knitting parallel to pressure direction is formed
Structure.But due to principal phase Nd in Nd-Fe-B magnets2Fe14B is tetragonal phase structure, and slip system number is less, thus is plastically deformed relatively tired
It is difficult.The prior art is mainly adjusted by alloying component to improve plastic history.Leonowicz etc. [Leonowicz M,
Davies H A.Effect of Nd content on induced anisotropy in hot deformed Fe-Nd-B
magnets[J].Mater.Lett.,1994,19(5):275-279] rare earth Nd content is have studied to anisotropy rare earth permanent magnet
The influence of body performance, it is indicated that the deformation process of alloy can be improved by improving content of rare earth.But largely it is distributed in the rare-earth phase of intergranular
Belong to non-magnetic phase, there is dilution effect, reduce the performance of magnet.Brown etc. [Brown D N, Smith B, Ma B M,
et al.The dependence of magnetic properties and hot workability of rare
earth-iron-boride magnets upon composition[J].IEEE Trans.Magn.,2004,40(4):
2895-2897] it have studied the influence of addition Rare-Earth Ce, Pr, Dy and metal Co, Ga to hot procedure and magnet performance, it is indicated that
The rare earth or alloying element of high level are conducive to deformation process, but unnecessary alloy is mainly distributed on crystal boundary and forms second
Phase, is non-magnetic phase, therefore same with magnetic effect is released, and reduces magnet performance.In addition, in hot pressing thermal deformation process, it is existing
Method cannot be overcome since rapidly quenched magnetic powder interface directly contacts, and frictional resistance is larger, and low melting point intergranular phase in thermal deformation process
The problem of contact surface that brings is extruded there are periodicity coarse grain, reduces magnet performance.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to it is nanocrystalline to provide a kind of anisotropy for adding graphene
Rare-earth permanent magnet and preparation method thereof, to overcome rare-earth permanent magnet slip system number less, magnetic powder contact surface inclement condition, plasticity
The defects of deformation is difficult, while further improve the magnetic property of rare-earth permanent magnet material.
Anisotropy nanocrystalline rare-earth permanent magnet of the present invention, the nanocrystalline rare-earth permanent magnet are by chemical formula
REaFe100-a-b-cBbTMcNanocrystalline with graphene and/or graphene microchip forms, wherein graphene and/or graphene microchip
Content be 0.01wt%~1wt%, the chemical formula REaFe100-a-b-cBbTMcIn, 28≤a≤33,0.9≤b≤1.35,
At least one of 0.15≤c≤7, RE Ce, Nd, Pr, Dy, in TM Ga, Co, Cu, Nb, Al, Zr, V, Si, Ti at least
It is a kind of.
The preparation method of anisotropy nanocrystalline rare-earth permanent magnet of the present invention, processing step are as follows：
With REaFe100-a-b-cBbTMcMagnetic powder and graphene or the quality that graphite microchip is raw material, graphene or graphite microchip
Percentage is 0.01%~1%, REaFe100-a-b-cBbTMcThe mass percent of magnetic powder is 99%~99.99%, will
REaFe100-a-b-cBbTMcMagnetic powder is uniformly mixed to obtain mixing magnetic powder with graphene or graphite microchip, will mixing magnetic powder room temperature,
3~10min is cold-pressed under 100MPa~700MPa pressure and obtains isotropism nanocrystalline magnet, or 400 DEG C~750 DEG C of temperature,
3~10min of hot pressing obtains isotropism nanocrystalline magnet under pressure 100MPa~700MPa；Again will cold pressing or hot pressing obtained by respectively to
Same sex nanocrystalline magnet carries out thermal deformation 2min~8min under 650 DEG C~850 DEG C of temperature, pressure 50MPa~250MPa, obtains
Anisotropy nanocrystalline rare-earth permanent magnet.
In the above method, the structure level number of the graphene is 1~10 layer, and graphene thickness is 0.8~20nm, and piece footpath is
50~1000nm.
In the above method, the structure level number of the graphene microchip is 11~100 layers, and thickness is 20~200nm, and piece footpath is
50~1000nm.
In the above method, the hot pressing, thermal deformation are carried out using sensing heating or discharge plasma sintering mode, are used
During sensing heating, hot pressing temperature is 550 DEG C~750 DEG C, hot pressing pressure is 100MPa~300MPa, and heat distortion temperature is 650 DEG C
~850 DEG C, thermal deformation pressure be 100MPa~250MPa；During using discharge plasma sintering, hot pressing temperature is 400 DEG C~650
DEG C, hot pressing pressure be 200MPa~700MPa, heat distortion temperature is 650 DEG C~750 DEG C, thermal deformation pressure be 50MPa~
200MPa。
In the above method, it is 65%~75% that when thermal deformation, which controls deflection, thus the speed of thermal deformation for 0.1mm/s~
0.5mm/s。
In the above method, thermal deformation can use following several ways：
A. restrained deformation in Free Transform (see Fig. 4) and mould (see Fig. 5)：Magnetic powder is loaded in hot pressing die and is pressed into
Fine and close base substrate, the demoulding are placed on shown in Fig. 4 or thermal change deformation are carried out in thermal deformation mould shown in Fig. 5, obtain anisotropy
Nanocrystalline composite.
B. carry on the back crimp (see Fig. 7)：Magnetic powder is loaded in hot pressing die (see Fig. 3) to the base substrate for being pressed into densification, the demoulding
Be placed in back of the body extruding deforming mould (see Fig. 7) and carry out back of the body crimp, the demoulding remove both ends inhomogeneous deformation area obtain it is each to
Different in nature radial orientation magnet ring.
Plus copper sheathing deformation method c.：Raw material magnetic powder is first cold-pressed into base in mould (see Fig. 3), moving back mould, to be placed on piece footpath bigger
(see Fig. 6) is provided with the thermal deformation mould of copper sheathing in pressed compact piece footpath, is then directly deformed in thermal deformation mould, formation is received
Rice anisotropic crystalline rare-earth permanent magnet.
In the method for the invention, raw material REaFe100-a-b-cBbTMcMagnetic powder can be bought by market, also can be by with lower section
It is prepared by method：
(1) according to chemical formula REaFe100-a-b-cBbTMcDispensing, in the chemical formula, 28≤a≤33,0.9≤b≤1.35,
At least one of 0.15≤c≤7, RE Ce, Nd, Pr, Dy element, TM Ga, Co, Cu, Nb, Al, Zr, V, Si, Ti element
At least one of；
(2) raw material for preparing step (1) carries out melting, is cast in after melting in water cooled copper mould, obtains REaFe100-a-b- cBbTMc-Alloy cast ingot；
(3) fast melt-quenching is carried out after alloy cast ingot is crushed and obtains REaFe100-a-b-cBbTMcRapidly quenched magnetic powder.
Compared with prior art, the invention has the advantages that：
It is 1. rich the present invention provides a kind of anisotropy nanocrystalline rare-earth permanent magnet containing graphene or graphene microchip
The rich type of rare earth permanent-magnetic material.
2. since graphene or graphene microchip have excellent electric conductivity, thermal conductivity, lubricity and mechanical property etc.
Feature, thus containing after a certain proportion of graphene or graphene microchip, the microstructure of magnet is obviously improved, and crystallite dimension is more
Small, pattern is more regular, and crystal grain orientation is more preferable, and comprehensive magnetic can have a distinct increment.
3. the preparation method of anisotropy nanocrystalline rare-earth permanent magnet of the present invention is with REaFe100-a-b-cBbTMcMagnetic powder with
Graphene or graphite microchip are raw material, and graphene or graphite microchip nano powder are evenly distributed on contact circle of rapidly quenched magnetic powder particle
Face, since it is with good greasy property so that the inhibition for mutually sliding or rotating between magnetic powder particle greatly reduces,
Be conducive to magnet hot-pressing densification and thermal deformation orientation process, overcome rare earth permanent-magnetic material RE-Fe-B magnet slip coefficients
The defects of mesh is less, and plastic deformation is difficult, so as to prepare more excellent performance of nanocrystalline rare-earth permanent magnet.
4. anisotropy nanocrystalline rare-earth permanent magnet of the present invention with the addition of graphene, graphene tool in preparation process
There are excellent conduction, heat conductivility, during discharge plasma sintering, since graphene powder being distributed between particle, enhancing
Intergranular electric conductivity, particle heating rate faster, reach the shortening of required temperature time, meanwhile, graphene good heat conduction
Property cause particle between heat transfer speed further speed up, magnet is also shorter the time required to integrally reaching consistent temperature, before deformation
Required soaking time further shortens, so as to suppress grain growth, is conducive to the raising of magnetic property；Using induction heating mode
When, the main heat conductivility excellent using graphene, shortens heating and soaking time, so as to suppress grain growth, is conducive to magnetic
The raising of performance.
5. the graphene of anisotropy nanocrystalline rare-earth permanent magnet of the present invention addition before being deformed after all the time with free
State form exists, and is not involved in crystalline phase composition, it, which is distributed between magnetic powder particle, can suppress crystal grain and grow up, and graphene have it is excellent
Mechanical property, the performances such as the compression strength of magnet can be lifted.
Brief description of the drawings
Fig. 1 for the microstructure of anisotropy nanocrystalline rare-earth permanent magnet made from embodiment 1 and energy spectrum analysis (figure a and
Scheme the microcosmic texture features figure of heat distortion magnet under b different multiplyings；Scheme c and be distributed shape appearance figure in intercrystalline for graphene；D is schemed for figure c
The energy spectral line scanning result figure of middle boxed area).
Fig. 2 is that the fracture apperance figure of anisotropy nanocrystalline rare-earth permanent magnet made from embodiment 2 (schemes a to be not added with stone
The magnet of black alkene, figure b are the magnet of addition 0.2wt% graphenes).
Fig. 3 is hot pressing schematic diagram.
Fig. 4 is free thermal deformation schematic diagram (it is before deforming, after figure b is deformation wherein to scheme a).
Fig. 5 is thermal deformation schematic diagram in mould.
Fig. 6 is to add copper sheathing thermal deformation schematic diagram (it is before deforming wherein to scheme a, and figure b is after deforming).
Fig. 7 is back of the body crimp schematic diagram.
In Fig. 4~Fig. 7,1- magnetic powders, 2- pressure heads；3- die sleeves, 4- hot-pressed magnets, 5- heat distortion magnets, 6- copper sheathings, 7- positioning
Ring.
Embodiment
Anisotropy nanocrystalline rare-earth permanent magnet and its system below by embodiment to addition graphene of the present invention
Preparation Method is described further.
Embodiment 1
(1) according to chemical formula Nd29.89Fe66.15Co5.93Ga0.64B0.92Dispensing, it is raw materials used to be more than 99.5% for purity
Rare earth neodymium, purity are 99.99% gallium, and purity is 99.9% cobalt, and purity is more than 99.9% pure iron, and Boron contents are
The ferro-boron of 19.3wt%；
(2) Nd that will have been configured29.89Fe66.15Co5.93Ga0.64B0.92Alloy raw material is put into intermediate frequency furnace melting rapid hardening earthenware
In crucible, reach 10 in vacuum-2During more than Pa, power transmission preheating, treats that vacuum reaches 10 again-2Stop vacuumizing after more than Pa
And high-purity Ar is filled with, the power adjustment of smelting furnace to monitor system is subjected to melting when Ar air pressures reach -0.05MPa in stove,
Stirring carries out refining 3min after raw material all fusing, and aluminium alloy is poured into water cooled copper mould after refining, is obtained
Nd29.89Fe66.15Co5.93Ga0.64B0.92Alloy cast ingot；
(3) by alloy cast ingot coarse crushing into the particle that particle diameter is 5~10mm, the ingot casting after then crushing is placed in vacuum electric
In water jacketed copper crucible in arc quick quenching furnace, open electric arc and melt, after ingot casting melts completely, melt (is turned by rotating molybdenum wheel
Speed is 35m/s, piece footpath 250mm) cooling obtain amorphous rapidly quenched magnetic powder Nd29.89Fe66.15Co5.93Ga0.64B0.92；
(4) 100 mesh sieve nets will be crossed after the further ball mill crushing of rapidly quenched magnetic powder, the 10g magnetic powders is then weighed and (adds with graphene
Dosage see the table below respectively, graphene parameter：The number of plies is 1~10 layer, and graphene thickness be 0.8~20nm, piece footpath is 50~
Ball milling 5min in vacuum planetary ball mill tank is put into after 500nm) mixing and obtains mixing magnetic powder, mixing magnetic powder is taken out under Ar gas shieldeds
And be put into preprepared hot pressing die, using discharging plasma sintering equipment at 600 DEG C of temperature, pressure 200MPa it is hot
Pressure obtains approaching the isotropic magnet of densification for 3 minutes, then by gained isotropic magnet in a manner of Free Transform (see Fig. 4),
Under 700 DEG C, pressure 150MPa, 2~4min is deformed with the rate of deformation of 0.18mm/s and (when graphene additive amount is different, is deformed
Easy degree has difference), deflection is 70%, obtains the anisotropy nanocrystalline rare-earth permanent magnetism of different graphene additive amounts
Body.
Comparative example 1
In addition to graphene is not added, in the same manner as shown in Example 1, Nd is prepared29.89Fe66.15Co5.93Ga0.64B0.92
Magnet.
Gained is not added with the magnetic property such as following table with the anisotropy nanocrystalline rare-earth permanent magnet of different graphene additive amounts：
The microstructure of gained anisotropy nanocrystalline rare-earth permanent magnet (0.2g graphenes) and energy spectrum analysis such as Fig. 1 institutes
Show, can be seen that magnet from Fig. 1 a and Fig. 1 b is formed by ribbon crystal grain stacking, and intergranular or bar interband are dispersed with Nd-rich phase
(white)；It can see from Fig. 1 c intergranular enlarged drawings, flaky graphite alkene is distributed in ribbon intercrystalline, and Fig. 1 d are corresponding power spectrum
Analysis, further confirms above-mentioned observed result.Add 1% graphene (0.1g) although under the conditions of magnet performance decline, mainly
It is attributed to substantial amounts of graphene and belongs to non-magnetic phase, dilute magnet performance, causes remanent magnetism and coercivity to decline, so that maximum magnetic flux
Energy product decreases；But after adding more graphene, magnet resistance in deformation process is obviously reduced, shorten deformation time,
Rock deformation pressure is reduced, new thinking is provided to prepare bulk heat distortion magnet later.
Embodiment 2
(1) according to chemical formula MM29.6Fe63.2Co6.0Ga0.6Al0.2B1.0(MM is mischmetal, mainly comprising Ce, Nd, Pr,
Micro Dy) dispensing, Ce is 49.8wt%, Nd 25wt%, Pr 25wt%, Dy 0.2wt% in raw materials used MM, purity
For 99.99% gallium, purity is 99.9% cobalt, and purity is 99.95% aluminium, and purity is more than 99.9% pure iron, Boron contents
For the ferro-boron of 19.3wt%；
(2) MM that will have been configured29.6Fe63.2Co6.0Ga0.6Al0.2B1.0Alloy raw material is put into intermediate frequency furnace melting rapid hardening earthenware
In crucible, reach 10 in vacuum-2During more than Pa, power transmission preheating, treats that vacuum reaches 10 again-2Stop vacuumizing after more than Pa
And high-purity Ar is filled with, the power adjustment of smelting furnace to monitor system is subjected to melting when Ar air pressures reach -0.05MPa in stove,
Stirring carries out refining 3min after raw material all fusing, and aluminium alloy is poured into water cooled copper mould after refining, is obtained
MM29.6Fe63.2Co6.0Ga0.6Al0.2B1.0Alloy cast ingot；
(3) by alloy cast ingot coarse crushing into the particle that particle diameter is 5~10mm, the ingot casting after then crushing is placed in vacuum electric
In water jacketed copper crucible in arc quick quenching furnace, open electric arc and melt, after ingot casting melts completely, melt (is turned by rotating molybdenum wheel
Speed is 28m/s, piece footpath 250mm) cooling obtain nanocrystalline rapidly quenched magnetic powder MM29.6Fe63.2Co6.0Ga0.6Al0.2B1.0；
(4) 100 mesh sieve nets will be crossed after the further ball mill crushing of rapidly quenched magnetic powder, then weighs the 10g magnetic powders and 0.02g graphite
Alkene (graphene parameter：The number of plies be 1~10 layer, graphene thickness be 0.8~20nm, and piece footpath is 50~500nm) mix after be put into
Mixing magnetic powder is obtained in vacuum planetary ball mill tank after ball milling 5min, mixing magnetic powder is taken out under Ar gas shieldeds and is put into prior preparation
In good hot pressing die, connect within 10 minutes using the hot pressing at 600 DEG C of temperature, pressure 200MPa of hot pressing thermal deformation equipment is sensed
Near fine and close isotropic magnet, then by gained isotropic magnet in a manner of Free Transform (see Fig. 4), in 750 DEG C, pressure
Under 100MPa, 4min is deformed with the rate of deformation of 0.15mm/s, deflection 75%, obtains the anisotropy nanometer of addition graphene
Brilliant rare-earth permanent magnet.
Comparative example 2
In addition to graphene is not added, according to method same as Example 2, MM is prepared29.6Fe63.2Co6.0Ga0.6Al0.2B1.0
Magnet.
Gained is not added with and with the addition of the magnetic property such as following table of the anisotropy nanocrystalline rare-earth permanent magnet of graphene：
It is micro- before and after contrast addition graphene shown in fracture apperance Fig. 2 of obtained anisotropy nanocrystalline rare-earth permanent magnet
See the change of structure, it can be seen that be not added with the magnet coarse grains of graphene, orientation is poor, and adds what is obtained after graphene
Magnet crystallite dimension is obviously reduced, and is orientated more regular, the hard magnetic phase RE of the nanocrystalline rare-earth permanent magnet2Fe14The crystallite dimension of B
It is less than or is at least less than 100nm (shown in corresponding diagram 2 (b)) in one direction, thus magnet performance is obviously improved.
Embodiment 3
(1) according to chemical formula Ce33Fe66.15Ga0.5B1.35Dispensing, raw materials used is the cerium that purity is more than 99.5%,
99.99% gallium, purity are more than 99.9% pure iron, and Boron contents are the ferro-boron of 19.3wt%；
(2) Ce that will have been configured33Fe66.15Ga0.5B1.35Alloy raw material is put into intermediate frequency furnace melting rapid hardening crucible,
Vacuum reaches 10-2During more than Pa, power transmission preheating, treats that vacuum reaches 10 again-2Stop vacuumizing and being filled with height after more than Pa
Pure Ar, carries out melting by the power adjustment of smelting furnace to monitor system when Ar air pressures reach -0.05MPa in stove, treats raw material
All stirring carries out refining 3min after fusing, and aluminium alloy is poured into water cooled copper mould after refining, is respectively obtained
Ce33Fe66.15Ga0.5B1.35Alloy cast ingot；
(3) by alloy cast ingot coarse crushing into the particle that particle diameter is 5~10mm, the ingot casting after then crushing is placed in vacuum electric
In water jacketed copper crucible in arc quick quenching furnace, open electric arc and melt, after ingot casting melts completely, melt (is turned by rotating molybdenum wheel
Speed is 33m/s, piece footpath 250mm) cooling obtain amorphous rapidly quenched magnetic powder Ce33Fe66.15Ga0.5B1.35；
(4) 100 mesh sieve nets will be crossed after the further ball mill crushing of rapidly quenched magnetic powder, the 10g magnetic powders is then weighed and (adds with graphene
Dosage see the table below respectively, graphene parameter：The number of plies is 1~10 layer, and graphene thickness be 0.8~20nm, piece footpath is 50~
1000nm) mixing, which is put into vacuum planetary ball mill tank after ball milling 5min, obtains mixing magnetic powder, takes out and is mixed under Ar gas shieldeds
Close magnetic powder and be put into preprepared hot pressing die, using discharging plasma sintering equipment (SPS) in 550 DEG C of temperature, pressure
Hot pressing obtains approaching the isotropic magnet of densification for 5 minutes under power 100MPa, then by gained isotropic magnet with Free Transform
Mode (see Fig. 4), under 700 DEG C, pressure 100MPa, 3~5min (graphene additive amounts are deformed with the rate of deformation of 0.15mm/s
When different, deformation easy degree has difference), deflection is 65%, obtains the anisotropy nanometer of different graphene additive amounts
Brilliant rare-earth permanent magnet.
Comparative example 3
In addition to graphene is not added, according to method same as Example 3, Ce is prepared33Fe66.15Ga0.5B1.35。
Gained is not added with the magnetic property such as following table with the anisotropy nanocrystalline rare-earth permanent magnet of different graphene additive amounts：
Embodiment 4
(1) according to chemical formula Nd29.8Fe68.6Ga0.4Ti0.15Si0.1B0.95, raw materials used is that purity is dilute more than 99.5%
Native neodymium, purity are 99.99% gallium, and purity is 99.5% titanium, and purity is 99.5% silicon, and purity is pure more than 99.9%
Iron, Boron contents are the ferro-boron of 19.3wt%；
(2) Nd that will have been configured29.8Fe68.6Ga0.4Ti0.15Si0.1B0.95Alloy raw material is put into intermediate frequency furnace melting rapid hardening
In crucible, reach 10 in vacuum-2During more than Pa, power transmission preheating, treats that vacuum reaches 10 again-2Stop taking out after more than Pa true
Sky is simultaneously filled with high-purity Ar, is melted the power adjustment of smelting furnace to monitor system when Ar air pressures reach -0.05MPa in stove
Refining, stirs after raw material all fusing and carries out refining 3min, aluminium alloy is poured into water cooled copper mould after refining, is obtained
Nd29.8Fe68.6Ga0.4Ti0.15Si0.1B0.95Alloy cast ingot；
(3) by alloy cast ingot coarse crushing into the particle that particle diameter is 5~10mm, the ingot casting after then crushing is placed in vacuum electric
In water jacketed copper crucible in arc quick quenching furnace, open electric arc and melt, after ingot casting melts completely, melt (is turned by rotating molybdenum wheel
Speed is 28m/s, piece footpath 250mm) cooling obtain nanocrystalline rapidly quenched magnetic powder Nd29.8Fe68.6Ga0.4Ti0.15Si0.1B0.95；
(4) 100 mesh sieve nets will be crossed after the further ball mill crushing of rapidly quenched magnetic powder, then weighs the 10g magnetic powders and 0.5g graphite
Alkene (graphene parameter：The number of plies be 1~10 layer, graphene thickness be 0.8~20nm, and piece footpath be 50~1000nm) mix be put into very
Ball milling 10min obtains mixing magnetic powder in null celestial body grinding jar, and mixing magnetic powder and being put into is taken out under Ar gas shieldeds and is ready in advance
Hot pressing die in, using induction heater, hot pressing obtains approaching each of densification for 5 minutes at 660 DEG C of temperature, pressure 200MPa
To same sex magnet, then by gained isotropic magnet in back of the body extrusion die (see Fig. 7), in 850 DEG C, 150~250MPa of pressure
Under (in the backward, resistance is bigger, and required extruding force is also bigger), 6min is deformed with the rate of deformation of 0.2mm/s, obtains outside diameter 30,
Internal diameter 24, the extrusion ring magnet of wall thickness 3mm.
Comparative example 4
In addition to graphene is not added, according to method same as Example 4, Nd is prepared29.8Fe68.6Ga0.4Ti0.15Si0.1B0.95
Magnet.
Gained is not added with and with the addition of the magnetic property such as following table of the anisotropy nanocrystalline rare-earth permanent magnet of graphene：
Embodiment 5
(1) according to chemical formula Ce28Fe66.22Nb0.1Cu0.05B1.08, it is raw materials used for cerium of the purity more than 99.5%, purity
For 99.6% niobium, purity is 99.9% copper, and purity is more than 99.9% pure iron, and Boron contents are the ferro-boron of 19.3wt%；
(2) Ce that will have been configured28Fe66.22Nb0.1Cu0.05B1.08Alloy raw material is put into intermediate frequency furnace melting rapid hardening crucible
It is interior, reach 10 in vacuum-2During more than Pa, power transmission preheating, treats that vacuum reaches 10 again-2Stop vacuumizing simultaneously after more than Pa
High-purity Ar is filled with, the power adjustment of smelting furnace to monitor system is subjected to melting when Ar air pressures reach -0.05MPa in stove, is treated
Stirring carries out refining 3min after raw material all melt, and aluminium alloy is poured into water cooled copper mould after refining, is obtained
Ce28Fe66.22Nb0.1Cu0.05B1.08Alloy cast ingot；
(3) by alloy cast ingot coarse crushing into the particle that particle diameter is 5~10mm, the ingot casting after then crushing is placed in vacuum electric
In water jacketed copper crucible in arc quick quenching furnace, open electric arc and melt, after ingot casting melts completely, melt (is turned by rotating molybdenum wheel
Speed is 30m/s, piece footpath 250mm) cooling obtain nanocrystalline rapidly quenched magnetic powder Ce28Fe66.22Nb0.1Cu0.05B1.08；
(4) 100 mesh sieve nets will be crossed after the further ball mill crushing of rapidly quenched magnetic powder, then weighs 10g magnetic powder 0.02g graphenes
(graphene parameter：The number of plies be 1~10 layer, graphene thickness be 0.8~20nm, and piece footpath is 50~1000nm) mix be put into vacuum
Mixing magnetic powder is obtained in planetary ball mill tank after ball milling 3min, preprepared is put into after mixing magnetic powder is taken out under Ar gas shieldeds
In mould, it is cold-pressed under room temperature, pressure 700MPa and obtains within 5 minutes finer and close isotropic magnet, then by gained isotropism
Magnet utilizes discharging plasma sintering equipment in a manner of adding copper sheathing thermal deformation (see Fig. 6), under 650 DEG C, pressure 50MPa, with
The rate of deformation deformation 8min of 0.1mm/s, deflection 68%, obtains anisotropy nanocrystalline rare-earth permanent magnet, its magnetic property is such as
Following table；
(5) 100 mesh sieve nets will be crossed after the further ball mill crushing of rapidly quenched magnetic powder, then weighs 10g magnetic powder 0.02g graphenes
(graphene parameter：The number of plies be 1~10 layer, graphene thickness be 0.8~20nm, and piece footpath is 50~1000nm) mix be put into vacuum
Ball milling 3min obtains mixing magnetic powder in planetary ball mill tank, mixing magnetic powder is taken out under Ar gas shieldeds, and be put into preprepared
In hot pressing die, using induction heater, hot pressing obtains the isotropism of densification for 5 minutes under 750 DEG C of temperature, pressure 200MPa
Magnet, then by gained isotropic magnet in a manner of adding copper sheathing thermal deformation (see Fig. 6), under 650 DEG C, pressure 100MPa, with
The rate of deformation deformation 6min of 0.1mm/s, deflection 67.8%, obtains anisotropy nanocrystalline rare-earth permanent magnet, its magnetic property
Such as following table：
Comparative example 5
In addition to graphene is not added, according to method (cold pressing+thermal deformation) same as Example 5, it is prepared
Ce28Fe66.22Nb0.1Cu0.05B1.08Magnet.
Gained is not added with the magnetic property such as following table with the anisotropy nanocrystalline rare-earth permanent magnet of different graphene additive amounts：
Embodiment 6
(1) according to chemical formula Nd29.8Fe62.24Co6.76Zr0.1V0.1B1.0, it is raw materials used for rare earth of the purity more than 99.5%
Neodymium, purity are more than 99% zirconium, and purity is 99.9% cobalt, and purity is 99.5% vanadium, and purity is more than 99.9% pure iron, boron
Content is the ferro-boron of 19.3wt%；
(2) Nd that will have been configured29.8Fe62.24Co6.76Zr0.1V0.1B1.0Alloy raw material is put into intermediate frequency furnace melting rapid hardening
In crucible, reach 10 in vacuum-2During more than Pa, power transmission preheating, treats that vacuum reaches 10 again-2Stop taking out after more than Pa true
Sky is simultaneously filled with high-purity Ar, is melted the power adjustment of smelting furnace to monitor system when Ar air pressures reach -0.05MPa in stove
Refining, stirs after raw material all fusing and carries out refining 3min, aluminium alloy is poured into water cooled copper mould after refining, is obtained
Nd29.8Fe62.24Co6.76Zr0.1V0.1B1.0Alloy cast ingot；
(3) by alloy cast ingot coarse crushing into the particle that particle diameter is 5~10mm, the ingot casting after then crushing is placed in vacuum electric
In water jacketed copper crucible in arc quick quenching furnace, open electric arc and melt, after ingot casting melts completely, melt (is turned by rotating molybdenum wheel
Speed is 30m/s, piece footpath 250mm) cooling obtain nanocrystalline rapidly quenched magnetic powder Nd29.8Fe62.24Co6.76Zr0.1V0.1B1.0；
(4) 100 mesh sieve nets will be crossed after the further ball mill crushing of rapidly quenched magnetic powder, then weighs 10g magnetic powder 0.02g graphenes
Microplate (graphene microchip parameter：The number of plies be 10~100 layers, thickness be 20~200nm, and piece footpath is 50~1000nm) mix be put into
Ball milling 10min obtains mixing magnetic powder in vacuum planetary ball mill tank, and mixing magnetic powder is taken out under Ar gas shieldeds and is put into prior preparation
In good hot pressing die, using induction heater, hot pressing obtains approaching densification for 5 minutes at 660 DEG C of temperature, pressure 200MPa
Isotropic magnet, then by gained isotropic magnet in a manner of Free Transform (see Fig. 4), under 700 DEG C, pressure 80MPa, with
The rate of deformation deformation 4min of 0.12mm/s, deflection 70%, obtains anisotropy nanocrystalline rare-earth permanent magnet.
Comparative example 6
In addition to graphene is not added, according to method same as Example 6, Nd is prepared29.8Fe62.24Co6.76Zr0.1V0.1B1.0
Magnet.
Gained is not added with the magnetic property of the anisotropy nanocrystalline rare-earth permanent magnet of different graphene microchip additive amounts such as
Following table：
Claims (6)
1. a kind of preparation method of anisotropy nanocrystalline rare-earth permanent magnet, the nanocrystalline rare-earth permanent magnet are by chemical formula
REaFe100-a-b-cBbTMcNanocrystalline with graphene and/or graphene microchip forms, wherein graphene and/or graphene microchip
Content be 0.01wt%~1wt%, the chemical formula REaFe100-a-b-cBbTMcIn, 28≤a≤33,0.9≤b≤1.35,
At least one of 0.15≤c≤7, RE Ce, Nd, Pr, Dy, in TM Ga, Co, Cu, Nb, Al, Zr, V, Si, Ti at least
It is a kind of, it is characterised in that processing step is as follows：
With REaFe100-a-b-cBbTMcMagnetic powder and graphene or the quality that graphene microchip is raw material, graphene or graphene microchip
Percentage is 0.01%~1%, REaFe100-a-b-cBbTMcThe mass percent of magnetic powder is 99%~99.99%, will
REaFe100-a-b-cBbTMcMagnetic powder is uniformly mixed to obtain mixing magnetic powder with graphene or graphene microchip, will mixing magnetic powder room temperature,
3~10min is cold-pressed under 100MPa~700MPa pressure and obtains isotropism nanocrystalline magnet, or 400 DEG C~750 DEG C of temperature,
3~10min of hot pressing obtains isotropism nanocrystalline magnet under pressure 100MPa~700MPa；Again will cold pressing or hot pressing obtained by respectively to
Same sex nanocrystalline magnet carries out thermal deformation 2min~8min under 650 DEG C~850 DEG C of temperature, pressure 50MPa~250MPa, obtains
Anisotropy nanocrystalline rare-earth permanent magnet；
The structure level number of the graphene is 1 layer~10 layers, and the structure level number of the graphene microchip is 11 layers~100 layers.
2. the preparation method of anisotropy nanocrystalline rare-earth permanent magnet according to claim 1, it is characterised in that the graphite
The thickness of alkene is 0.8nm~20nm, and piece footpath is 50nm~1000nm.
3. the preparation method of anisotropy nanocrystalline rare-earth permanent magnet according to claim 1, it is characterised in that the graphite
The thickness of alkene microplate is 20nm~200nm, and piece footpath is 50nm~1000nm.
4. the preparation method of anisotropy nanocrystalline rare-earth permanent magnet according to any claim in claims 1 to 3, its
Being characterized in that the hot pressing, thermal deformation is carried out using sensing heating or discharge plasma sintering mode, during using sensing heating,
Hot pressing temperature is 550 DEG C~750 DEG C, hot pressing pressure is 100MPa~300MPa, and heat distortion temperature is 650 DEG C~850 DEG C, thermal change
Shape pressure is 100MPa~250MPa；During using discharge plasma sintering, hot pressing temperature is 400 DEG C~650 DEG C, hot pressing pressure is
200MPa~700MPa, heat distortion temperature is 650 DEG C~750 DEG C, thermal deformation pressure is 50MPa~200MPa.
5. the preparation method of anisotropy nanocrystalline rare-earth permanent magnet according to any claim in claims 1 to 3, its
The speed for being characterized in that thermal deformation is 0.1mm/s~0.5mm/s.
6. the preparation method of anisotropy nanocrystalline rare-earth permanent magnet according to claim 4, it is characterised in that thermal deformation
Speed is 0.1mm/s~0.5mm/s.
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| CN107452456B (en) * | 2017-08-29 | 2019-06-28 | 钢铁研究总院 | A kind of high-intensity and high-tenacity permanent magnet and preparation method thereof |
| WO2019056643A1 (en) * | 2017-09-20 | 2019-03-28 | 江民德 | Method for producing neodymium-iron-boron composite magnetic material |
| CN112071543B (en) * | 2020-08-05 | 2022-04-22 | 四川大学 | High-coercivity rare earth permanent magnet and preparation method thereof |
| CN111986913B (en) * | 2020-09-23 | 2022-03-11 | 赣州富尔特电子股份有限公司 | Method for improving performance of sintered neodymium-iron-boron magnet |
| CN112670048B (en) * | 2020-12-11 | 2023-02-03 | 东莞市嘉达磁电制品有限公司 | Partial pressure sintering manufacturing method of neodymium iron boron magnet |
| CN112670047B (en) * | 2020-12-11 | 2023-02-03 | 东莞市嘉达磁电制品有限公司 | High-temperature-resistant neodymium-iron-boron magnet and preparation method thereof |
| CN113035558A (en) * | 2021-03-12 | 2021-06-25 | 清华大学 | Thermal deformation neodymium iron boron magnet and preparation method thereof |
| CN113053606A (en) * | 2021-03-16 | 2021-06-29 | 东莞金坤新材料股份有限公司 | Graphene rare earth permanent magnetic material and preparation method thereof |
| CN113539597A (en) * | 2021-06-18 | 2021-10-22 | 北京工业大学 | Anisotropic nanocrystalline cobalt-based rare earth permanent magnet and preparation method thereof |
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